Acyl mercapto-triazolyl derivatives and the use thereof as microbicides

ABSTRACT

The present invention provides the composition for novel acyl-mercapto-triazolyl derivatives, and the acid addition salts and metal salt complexes thereof; a process for their preparation; and a method for their use as microbicides.

This application is a divisional of U.S. application Ser. No. 09/180,055 filed on Oct. 27, 1998, now U.S. Pat. No. 6,051,592, which is a national stage application under 35 USC 371 of PCT/EP97/01997, filed on Apr. 21, 1997.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to novel acyl-mercapto-triazolyl derivatives, to a process for their preparation and to their use as microbicides.

BACKGROUND OF THE INVENTION

It is already known that numerous triazolyl derivatives have fungicidal properties (cf. EP-A 0 015 756, EP-A 0 040 345, EP-A 0 052 424, EP-A 0 061 835, EP-A 0 297 345, EP-A 0 094 564, EP-A 0 196 038, EP-A 0 267 778, EP-A 0 378 953, EP-A 0 044 605, EP-A 0 069 442, EP-A 0 055 833, EP-A 0 301 393, DE-A 2 324 010, DE-A 2 737 489, DE-A 2 551 560, EP-A 0 065 485, DE-A 2 735 872, EP-A 0 234 242, DE-A 2 201 063, EP-A 0 145 294 and DE-A 3 721 786). The activity of these substances is good, but in some cases leaves something to be desired at low application rates.

DETAILED DESCRIPTION OF THE INVENTION

This invention, accordingly, provides novel acyl-mercapto-triazolyl derivatives of the formula

in which

R represents alkyl, halogenoalkyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, alkylamino or optionally substituted arylamino and

R¹ represents a radical of the formula

in

R² and R³ are identical or different and each represent optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aralkenyl, optionally substituted aroxyalkyl, optionally substituted aryl or optionally substituted heteroaryl,

or

R¹ represents a radical of the formula

in which

R⁴ represents alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally halogen-substituted cycloalkyl having 3 to 7 carbon atoms, naphthyl or phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, nitro, phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, and

R⁵ represents phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms,

or

R¹ represents a radical of the formula

in which

R⁶ and R⁷ independently of one another each represent hydrogen or alkyl having 1 to 6 carbon atoms,

X¹ represents halogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 4 carbon atoms, phenyl, phenoxy, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms or represents halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, and

m represents the numbers 0, 1 or 2,

or

R¹ represents a radical of the formula

in which

R⁸ and R⁹ independently of one another each represent hydrogen or alkyl having 1 to 6 carbon atoms,

X² represents halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms or phenyl,

n represents the numbers 0 or 1 and

p represents the numbers 0, 1 or 2,

or

R¹ represents a radical of the formula

in which

R¹⁰ represents alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, optionally substituted aryl or represents optionally substituted aralkyl,

or

R¹ represents a radical of the formula

in which

R¹¹ represents hydrogen, alkyl or optionally substituted cycloalkyl,

X³ represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms.

q represents the numbers 0, 1, 2 or 3 and

Y¹ represents an oxygen atom, a CH₂ group or a direct bond,

or

R¹ represents a radical of the formula

in which

R¹² represents alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, cycloalkyl having 3 to 7 carbon atoms which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, optionally halogen-substituted phenyl or represents optionally halogen-substituted benzyl,

X⁴ represents halogen, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms,

r represents the numbers 0, 1, 2 or 3 and

Y² represents an oxygen atom or represents a CH₂ group,

or

R¹ represents a radical of the formula

in which

A represents alkanediyl having 2 or 3 carbon atoms which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms,

X⁵ represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms

and

s represents the numbers 0, 1, 2 or 3,

or

R¹ represents a radical of the formula

in which

R¹³ represents alkyl having 1 to 10 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, fluoroalkoxyalkyl having 1 to 4 carbon atoms in the fluoroalkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, cycloalkyl having 3 to 7 carbon atoms which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety, optionally halogen-substituted phenyl or represents optionally halogen-substituted phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety,

X⁶ represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, and

t represents the numbers 0, 1, 2 or 3,

or

R¹ represents a radical of the formula

in which

R¹⁴ represents alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, cycloalkyl having 3 to 7 carbon atoms which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alklyl moiety, optionally halogen-substituted phenyl or represents optionally halogen-substituted benzyl,

X⁷ represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms,

u represents the numbers 0, 1, 2 or 3 and

Y³ represents an oxygen atom or represents a CH₂ group,

or

R¹ represents a radical of the formula

in which

R¹⁵ represents alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, optionally substituted aryl or represents optionally substituted aralkyl,

X⁸ represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms, or represents phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms and

v represents the numbers 0, 1, 2 or 3,

and acid addition salts and metal salt complexes thereof.

A large number of the substances according to the invention contain one or more asymmetrically substituted carbon atoms. They may therefore be obtained in the form of optical isomers. The present invention relates both to the individual isomers and to mixtures thereof.

Furthermore, it has been found that acyl-mercapto-triazolyl derivatives of the formula (I) and acid addition salts and metal salt complexes thereof are obtained when mercapto-triazoles of the formula

in which

R¹ is as defined above

 are either

a) reacted with acyl halides of the formula

R¹⁶—CO—Hal  (III)

in which

R¹⁶ represents alkyl, halogenoalkyl, optionally substituted aryl or optionally substituted aralkyl and

Hal represents chlorine or bromine

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

 or

b) reacted with halogenoformates of the formula

in which

R¹⁷ represents alkyl and

Hal¹ represents chlorine or bromine,

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

 or

c) reacted with isocyanates of the formula

R¹⁸—N═C═O  (V)

in which

R¹⁸ represents alkyl or represents optionally substituted aryl,

if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent,

and, if appropriate, an acid or a metal salt is subsequently added to the resulting compounds of the formula (I).

Finally, it has been found that the novel acyl-mercapto-triazolyl derivatives of the formula (I) and acid addition salts and metal salt complexes thereof have very good microbicidal properties and can be used both in crop protection and in the protection of materials for controlling undesirable microorganisms.

Surprisingly, the substances according to the invention have better microbicidal activity, in particular fungicidal activity, than the constitutionally most similar compounds of the same direction of action.

The formula (I) provides a general definition of the acyl-mercapto-triazolyl derivatives according to the invention.

R preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 12 carbon atoms, straight-chain or branched alkylamino having 1 to 14 carbon atoms or represents phenylamino which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms.

R¹ preferably represents a radical of the formula

in which

R² preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, it being possible for these radicals to be mono- to tetrasubstituted by identical or different substituents selected from the group consisting of halogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4 carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbon atoms,

 or

preferably represents straight-chain or branched alkenyl having 2 to 6 carbon atoms, it being possible for each of these radicals to be mono- to trisubstittited by identical or different substituents selected from the group consisting of halogen, alkoxy having 1 to 4 carbon atoms and cycloalkyl having 3 to 7 carbon atoms,

 or

preferably represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, cyano and alkyl having 1 to 4 carbon atoms,

 or

preferably represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and 2 to 4 carbon atoms in the alkenyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aryl having 6 to 10 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents an optionally benzo-fused five- or six-membered heteroaromatic radical having 1 to 3 hetero atoms, such as nitrogen, sulphur and/or oxygen, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms, hydroxyalkinyl having 3 to 8 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl, halogenoalkoxy and halogenoalkylthio having in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms such as fluorine or chlorine atoms, formyl, dialkoxymethyl having 1 or 2 carbon atoms in each alkoxy group, acyl having 2 to 4 carbon atoms alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety, nitro and cyano, and

R³ preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, it being possible for these radicals to be mono- to tetrasubstituted by identical or different substituents selected from the group consisting of halogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4 carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbon atoms,

 or

preferably represents straight-chain or branched alkenyl having 2 to 6 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen. alkoxy having 1 to 4 carbon atoms and cycloalkyl having 3 to 7 carbon atoms,

 or

preferably represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, cyano and alkyl having 1 to 4 carbon atoms,

 or

preferably represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and 2 to 4 carbon atoms in the alkenyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety, it being possible for each of the aryl moieties to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different h alogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkyethio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents aryl haning 6 to 10 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 t o 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and cyano,

 or

preferably represents an optionally benzo-fused five- or six-membered heteroaromatic radical having 1 to 3 hetero atoms, such as nitrogen, sulphur and/or oxygen, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms , hydroxyalkinyl having 3 to 8 carbon atoms, alkoxy having 1 o r 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl, halogenoalkoxy and halogenoalkylthio having in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine or chlorine atoms, formyl, dialkoxymethyl having 1 or 2 carbon atoms in each alkoxy group, acyl having 2 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety, nitro and cyano.

R¹ furthermore preferably represents a radical of the formula

in which

R⁴ preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine, represents naphthyl or represents phenyl which may be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio, and

R⁵ preferably, represents phenyl which may be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, myethyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio.

R¹ furthermore preferably represents a radical of the formula

in which

R⁶ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

R⁷ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

X¹ preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, phenyl, phenoxy, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy or trifluoromethylthio and

m also preferably represents the numbers 0, 1 or 2,

where X¹ may represent identical or different radicals if m represents 2.

R¹ furthermore preferably represents a radical of the formula

in which

R⁸ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

R⁹ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

X² preferably represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, trichloromethoxy, trifluoromethoxy, difluoromethoxy, difluorochloromethoxy or phenyl,

n also preferably represents the numbers 0 or 1 and

p also preferably represents the numbers 0, 1 or 2,

where X² may represent identical or different radicals if p represents 2.

R¹ furthermore preferably represents a radical of the formula

in which

R¹⁰ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, straighit-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, represents cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, represents phenyl, benzyl or phenethyl, it being possible for each of the three last-mentioned radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of to halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms or phenoxy which is optionally substituted by halogen and/or alkyl having 1 to 4 carbon atoms.

R¹ furthermore preferably represents a radical of the formula

in which

R¹¹ preferably represents hydrogen, straigyht-chain or branched alkyl having 1 to 1 2 carbon atoms or represents cycloalkyl having 3 to 7 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms.

X³ preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy,

q preferably represents the numbers 0, 1, 2 or 3, where X³ represents identical or different radicals if q represents 2 or 3, and

Y¹ preferably represents an oxygen atom, a CH₂ group or a direct bond.

R¹ furthermore preferably represents a radical of the formula

in which

R¹² preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, fluoroalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 3 carbon atoms in the alkyl moiety, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents benzyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁴ preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl or represents plienoxy which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl,

r preferably represents the numbers 0, 1, 2 or 3, where X⁴ represents identical or different radicals if r represents 2 or 3 and

Y² preferably represents an oxygen atom or represents a CH₂ group.

R¹ furthermore preferably represents a radical of the formula

in which

A preferably represents alkanediyl having 2 or 3 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl and tert-butyl,

X⁵ preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, difluoromethoxy, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl and/or represents phenoxy which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl and

s preferably represents the numberts 0, 1, 2 or 3, where X⁵ represents identical or different radicals if s represents 2 or 3,

R¹ furthermore preferably represents a radical of the formula

in which

R¹³ preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, fluoroalkoxyalkyl having 1 to 3 carbon atoms and 1 to 5 fluorine atoms in the fluoroalkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety, cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 3 carbon atoms in the alkyl moiety, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁶ preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl or represents phenoxy which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl and

t preferably represents the numbers 0, 1, 2 or 3, where X⁶ represents identical or different radicals if t represents 2 or 3,

R¹ furthermore preferably represents a radical of the formula

in which

R¹⁴ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, fluoroalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 3 carbon atoms in the alkyl moiety, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents benzyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁷ preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trinluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl or represents phenoxy which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl,

u preferably represents the numbers 0, 1, 2 or 3, where X⁷ represents identical or different radicals if u represents 2 or 3, and

Y³ preferably represents an oxygen atom or represents a CH₂ group.

R¹ furthermore also preferably represents a radical of the formula

in which

R¹⁵ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms with 1 to 5 halogen atoms, alkoxy having 1 to 4 carbon atoms and halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms or represents phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 4 carbon atoms and halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms,

X⁸ preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl or represents phenoxy which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine and methyl and

v preferably represents the numbers 0, 1, 2 or 3, where X⁸ represents identical or different radicals if v represents 2 or 3,

R particularly preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl, phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl, straight-chain or branched alkoxy having 1 to 10 carbon atoms, straight-chain or branched alkylamino having 1 to 12 carbon atoms or represents phenylamino which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl,

R¹ particularly preferably represents a radical of the formula

in which

R² particularly preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, it being possible for these radicals to be mono- to teirasubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, alkoximino having 1 or 2 carbon atoms in the alkoxy moiety, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,

 or

particularly preferably represents straight-chain or branched alkenyl having 2 to 5 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,

 or

particularly preferably represents cycloalkyl having 3 to 6 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, isopropyl and tert-butyl,

 or

particularly preferably represents phenylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlordifluoromethoxy, difluoromethoxy, chlorodifuoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenylalkenyl having 2 to 4 carbon atoms in the alkenyl moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenyl which may be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl, benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, formyl, dimethoxymethyl, acetyl and propionyl, and

R³ particularly preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, it being possible for these radicals to be mono- to tetrasubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, alkoximino having 1 or 2 carbon atoms in the alkoxy moiety, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,

 or

particularly preferably represents straight-chain or branched alkenyl having 2 to 5 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,

 or

particularly preferably represents cycloalkyl having 3 to 6 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, isopropyl and tert-butyl,

 or

particularly preferably represents plienylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenyoalkenyl having 2 to 4 carbon atoms in the alkenyi moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chorodifluorometthoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenoxyalkyl having 1 to 4 carbon atoms in the straight-chain or branched oxyalkyl moiety, it being possible for the phenyl moiety to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents phenyl which m ay be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinometbyl, 1-methoximinoethyl, nitro and cyano,

 or

particularly preferably represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, purrolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl, benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, triofluoromethoxy, trifluoromethylthio, chlorodifiuoromethoxy, chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, formyl, dimethoxymethyl, acetyl and propionyl,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R⁴ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl fluoro-tert-butyl, difluoro-tert-butyl, cycloalkyl having, 3 to 6 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine, represents naphthyl or represents phenyl which may be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio, and

R⁵ particularly preferably represents phenyl which may be mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, isobutyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R⁶ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

R⁷ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

X¹ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, phenyl, phenoxy, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy or trifluoromethylihio and

m also particularly preferably represents the numbers 0, 1 or 2,

it being possible for X¹ to represent identical or different radicals if m represents 2,

R¹ particularly preferably represents a radical of the formula

in which

R⁸ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

R⁹ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl,

X² particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, trichloromeihoxy, trifluoromethoxy, difluoromethoxy, difluorochloromethoxy or phenyl,

n also particularly preferably represents the numbers 0 or 1 and

p also particularly preferably represents the numbers 0, 1 or 2,

it being possible for X² to represent identical or different radicals if p represents 2,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R¹⁰ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, halogenoalkyl having 1 to 4 carbon atoms and 1 to 3 fluorine, chlorine and/or bromine atoms, cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl, and also represents phenyl, benzyl or phenethyl, it being possible for each of the three last-mentioned radicals to be mono- to trisubstituted in the phenyl moiety by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl and phenoxy.

R¹ furthermore particularly preferably represents a radical of the formula

in which

R¹¹ particularly preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and ethyl,

X³ particularly preferably represents fluorine, chlorine, bromine, methyl, methoxy, methyitlilo, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy,

q also particularly preferably, represents the numbers 0, 1, 2 or 3, it being possible for X³ to represent identical or different radicals if q represents 2 or 3 and

Y¹ also particularly preferably represents an oxygen atom, a CH₂ group or a direct bond,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R¹² particularly preferably represents methyl, isopropyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl, represents cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 or 2 carbon atoms in the alkyl moiety, represents phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents benzyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁴ particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, tert-butyl, methoxy, methyltihio, trichloromethyl, trifluoromethyl trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy,

r also particularly preferably represents the numbers 0, 1, 2 or 3, it being possible for X⁵ to represent identical or different radicals if r represents 2 or 3 and

Y² also particularly preferably represents an oxygen atom or represents a CH₂ group.

R¹ furthermore particularly preferably represents a radical of the formula

in which

A particularly preferably represents alkanediyl having 2 or 3 carbon atoms which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl and tert-butyl,

X⁵ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, difluoromethoxy, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl and/or represents phenoxy which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl and

s also particularly preferably represents the numbers 0, 1, 2 or 3, it being possible for X⁵ to represent identical or different radicals if s represents 2 or 3,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R¹³ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, fluoroalkoxyalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine atoms in the fluoroalkoxy moiety and 1 or 2 carbon atoms in the alkyl moiety, cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl, represents cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 or 2 carbon atoms in the alkyl moiety, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents benzyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁶ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, metlioxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethiylthio, phenyl or phenoxy and

t also particularly preferably represents the numbers 0, 1, 2 or 3, it being possible for X⁶ to represent identical or different radicals if t represents 2 or 3,

R¹ furthermore particularly preferably represents a radical of the formula

in which

R¹⁴ particularly preferably represents methyl, isopropyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and methyl, represents cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 or 2 carbon atoms in the alkyl moiety, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine or represents benzyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine and bromine,

X⁷ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, methylthio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, phenyl or phenoxy,

Y³ also particularly preferably represents an oxygen atom or represents a CH₂ group, and

u also particularly preferably represents the numbers 0, 1, 2 or 3, where X⁷ represents identical or different radicals if u represents 2 or 3.

R¹ moreover also preferably represents a radical of the formula

in which

R¹⁵ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, phenyl which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl, ethyl, trifluoromethyl, trichloromethyl, methoxy, ethoxy, trifluoromethoxy and difluoromethoxy or represents phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety which is optionally mono- or disubstituted in the phenyl moiety by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, trichloromethyl, methoxy, ethoxy, trifluoromethoxy and difluoromethoxy,

X⁸ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, niethoxy, methyltliio, trichloromethyl, trifluoromethyl, trifluoromethoxy, difuoromethoxy, trifluoromethylthio, phenyl or phenoxy, and

v also particularly preferably represents the numbers 0, 1, 2 or 3, it being possible for X⁸ to represent identical or different radicals if v represents 2 or 3.

Preferred compounds according to the invention are also addition products of acids and those acyl-mercapto-triazolyl derivatives of the formula (I) in which R and R¹ have those meanings which have been mentioned as being particularly preferred for these substituents,

The acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydrocarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and also sulphonic acids, such as, for example, p-toluenesulphonic acid and 1.5-naphthalenedisulphonic acid, and also saccharin and thiosaccharin,

Preferred compounds according to the invention are moreover addition products of salts of metals of main groups II to IV and sub-groups I and II and also IV to VIII of the Periodic Table of the Elements and those acyl-mercapto-triazolyl derivatives of the formula (I) in which R and R¹ have those meanings which have been mentioned as being preferred for these substituents,

Particular preference is given here to salts of copper, zinc, manganese, magnesium, tin, iron and nickel. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Acids of this kind which are particularly preferred in this context are hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulphuric acid.

The mercapto-triazoles required as starting materials in the preparation of the substances according to the invention can be present in the “mercapto” form of the formula

or in the tautomeric “thiono” form of the formula

It can therefore not be excluded that some or all of the substances according to the invention are derived from the “thiono” form of the formula (IIa). This means that the substances according to the invention are either present as substances of the formula

or of the formula

or as mixtures of substances of the formulae (I) and (Ia). For simplicity, only the structure of the “mercapto” form is given in each case.

Examples of substances according to the invention include the acyl-mercapto-triazolyl derivatives listed in the tables below.

TABLE 1 (1b)

R² R³ R

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —C₂H₅

—C(CH₃)₃

—C(CH₃)₃ —O—CH₃

—C(CH₃)₃

—C(CH₃)₃ —NH—CH₃

—C(CH₃)₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —C₂H₅

—C(CH₃)₃

—C(CH₃)₃ —OCH₃

—C(CH₃)₃

—C(CH₃)₃ —NH—CH₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —C₂H₅

—C(CH₃)₃

—C(CH₃)₃ —NH—CH₃

—CH₃

—C₂H₅

—NH—CH₃

—C₄H₉-n —CH₃

—C₄H₉-n —C₂H₅

—C₄H₉-n

—C₄H₉-n —NH—CH₃

—CH₃

—OCH₃

—NH—CH₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —C₂H₅

—C(CH₃)₃

—C(CH₃)₃ —OCH₃ Cl₂CH—CCl₂—CH₂— —C(CH₃)₃ —CH₃ Cl₂CH—CCl₂—CH₂— —C(CH₃)₃ —C₂H₅ Cl₂CH—CCl₂—CH₂—

—CH₃ Cl₂CH—CCl₂—CH₂—

—C₂H₅ Cl₂CH—CCl₂—CH₂—

—CH₃ Cl₂CH—CCl₂—CH₂—

—OCH₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —C₂H₅

—CH₃

—C₂H₅

—C₂H₅

—C₂H₅

—CH₃ Cl₂CH—CCl₂—

—CH₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃ —CH₃

—C(CH₃)₃

TABLE 2 (1c)

R⁴ R⁵ R

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃ —CH₃

—CH₃ —CH₃

—CH₃ —CH₃

—CH₃ —C(CH₃)₃

—CH₃

—CH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃ —CH₃

—OCH₃ —CH₃

—OCH₃ —CH₃

—OCH₃ —C(CH₃)₃

—OCH₃

—OCH₃

TABLE 3 (Id)

R⁶ R⁷ R X¹ _(m) —CH₃ —CH₃ —CH₃ 4-Br —CH₃ —CH₃ —CH₃ 4-F —CH₃ —CH₃ —CH₃ 2,4-Cl₂ —CH₃ H —CH₃ 4-Cl —CH₃ —CH₃ —CH₃ — —CH₃ —CH₃ —CH₃ 4-CH₃ —CH₃ —CH₃ —CH₃ 2-F, 4-Cl —C₂H₅ H —CH₃ 4-Cl —C₂H₅ —C₂H₅ —CH₃ 4-Cl —C₃H₇-n H —CH₃ 4-Cl —C₂H₅ H —CH₃ 2,4-Cl₂ —C₂H₅ H —CH₃ 4-F —C₂H₅ H —CH₃ 4-Br —C₂H₅ H —CH₃

—C₂H₅ H —CH₃ 4-C₄H₉-t —C₃H₇-i H —CH₃ 4-Cl —C₅H₁₁-n H —CH₃ 4-Cl —CH₃ —CH₃ —CH₃

—CH₃ —CH₃ —CH₃ 4-C₄H₉-t —C₄H₉-n H —CH₃ 4-Cl —C₄H₉-i H —CH₃ 4-Cl —CH₃ —C₂H₅ —CH₃ 4-Cl —CH₃ —CH₃ —OCH₃ 4-Cl —CH₃ —CH₃ —OCH₃ 4-Br —CH₃ —CH₃ —OCH₃ 4-F —CH₃ —CH₃ —OCH₃ 2,4-Cl₂ —CH₃ H —OCH₃ 4-Cl —CH₃ —CH₃ —OCH₃ — —CH₃ —CH₃ —OCH₃ 4-CH₃ —CH₃ —CH₃ —OCH₃ 2-F, 4-Cl —C₂H₅ H —OCH₃ 4-Cl —C₂H₅ —C₂H₅ —OCH₃ 4-Cl —C₃H₇-n H —OCH₃ 4-Cl —C₂H₅ H —OCH₃ 2,4-Cl₂ —C₂H₅ H —OCH₃ 4-F —C₂H₅ H —OCH₃ 4-Br —C₂H₅ H —OCH₃

—C₂H₅ H —OCH₃ 4-C₄H₉-t —C₃H₇-i H —OCH₃ 4-Cl —C₅H₁₁-n H —OCH₃ 4-Cl —CH₃ —CH₃ —OCH₃

—CH₃ —CH₃ —OCH₃ 4-C₄H₉-t —C₄H₉-n H —OCH₃ 4-Cl —C₄H₉-i H —OCH₃ 4-Cl —CH₃ —C₂H₅ —OCH₃ 4-Cl —CH₃ —CH₃ —CH₃ 2-Cl —CH₃ —CH₃ —CH₃ 2,3-Cl₂ —CH₃ —CH₃ —CH₃ 4-CF₃ —CH₃ —CH₃ —CH₃ 4-OCF₃ —CH₃ —CH₃ —CH₃ 4-Cl

TABLE 4 (Ie)

R⁸ R⁹ R X² _(p) n —CH₃ —CH₃ —CH₃ 4-Br 0 —CH₃ —CH₃ —CH₃ 4-F 0 —CH₃ —CH₃ —CH₃ 2,4-Cl₂ 0 —CH₃ H —CH₃ 4-Cl 0 —CH₃ —CH₃ —CH₃ — 0 —CH₃ —CH₃ —CH₃ 4-CH₃ 0 —CH₃ —CH₃ —CH₃ 2-F, 4-Cl 0 —C₂H₅ H —CH₃ 4-Cl 0 —C₂H₅ —C₂H₅ —CH₃ 4-Cl 0 —C₃H₇-n H —CH₃ 4-Cl 0 —C₂H₅ H —CH₃ 2,4-Cl₂ 0 —C₂H₅ H —CH₃ 4-F 0 —C₂H₅ H —CH₃ 4-Br 0 —C₂H₅ H —CH₃ 4-NO₂ 0 —C₂H₅ H —CH₃ 4-C₄H₉-t 0 —C₃H₇-i H —CH₃ 4-Cl 0 —C₅H₁₁-n H —CH₃ 4-Cl 0 —CH₃ —CH₃ —CH₃ 4-CN 0 —CH₃ —CH₃ —CH₃ 4-C₄H₉-t 0 —C₄H₉-n H —CH₃ 4-Cl 0 —C₄H₉-i H —CH₃ 4-Cl 0 —CH₃ —C₂H₅ —CH₃ 4-Cl 0 —CH₃ —CH₃ —OCH₃ 4-Cl 0 —CH₃ —CH₃ —OCH₃ 4-Br 0 —CH₃ —CH₃ —OCH₃ 4-F 0 —CH₃ —CH₃ —OCH₃ 2,4-Cl₂ 0 —CH₃ H —OCH₃ 4-Cl 0 —CH₃ —CH₃ —OCH₃ — 0 —CH₃ —CH₃ —OCH₃ 4-CH₃ 0 —CH₃ —CH₃ —OCH₃ 2-F, 4-Cl 0 —C₂H₅ H —OCH₃ 4-Cl 0 —C₂H₅ —C₂H₅ —OCH₃ 4-Cl 0 —C₃H₇-n H —OCH₃ 4-Cl 0 —C₂H₅ H —OCH₃ 2,4-Cl₂ 0 —C₂H₅ H —OCH₃ 4-F 0 —C₂H₅ H —OCH₃ 4-Br 0 —C₂H₅ H —OCH₃ 4-NO₂ 0 —C₂H₅ H —OCH₃ 4-C₄H₉-t 0 —C₃H₇-i H —OCH₃ 4-Cl 0 —C₅H₁₁-n H —OCH₃ 4-Cl 0 —CH₃ —CH₃ —OCH₃ 4-CN 0 —CH₃ —CH₃ —OCH₃ 4-C₄H₉-t 0 —C₄H₉-n H —OCH₃ 4-Cl 0 —C₄H₉-i H —OCH₃ 4-Cl 0 —CH₃ —C₂H₅ —OCH₃ 4-Cl 0 —CH₃ —CH₃ —CH₃ 4-OCH₃ 0 —CH₃ —CH₃ —CH₃ 2-OCH₃ 0 —CH₃ —CH₃ —CH₃ 2-CF₃ 0 —CH₃ —CH₃ —CH₃ 4-CF₃ 0 —CH₃ —CH₃ —CH₃ 2-OCF₃ 0 —CH₃ —CH₃ —CH₃ 2-OCHF₂ 0 —CH₃ —CH₃ —CH₃ 4-OCF₃ 0 —CH₃ —CH₃ —OCH₃ 4-OCH₃ 0 —CH₃ —CH₃ —OCH₃ 2-OCH₃ 0 —CH₃ —CH₃ —OCH₃ 2-CF₃ 0 —CH₃ —CH₃ —OCH₃ 4-CF₃ 0 —CH₃ —CH₃ —OCH₃ 2-OCF₃ 0 —CH₃ —CH₃ —OCH₃ 2-OCHF₂ 0 —CH₃ —CH₃ —OCH₃ 4-OCF₃ 0 —CH₃ —CH₃ —CH₃ 4-Br 1 —CH₃ —CH₃ —CH₃ 4-F 1 —CH₃ —CH₃ —CH₃ 2,4-Cl₂ 1 —CH₃ H —CH₃ 4-Cl 1 —CH₃ —CH₃ —CH₃ — 1 —CH₃ —CH₃ —CH₃ 4-CH₃ 1 —CH₃ —CH₃ —CH₃ 2-F, 4-Cl 1 —C₂H₅ H —CH₃ 4-Cl 1 —C₂H₅ —C₂H₅ —CH₃ 4-Cl 1 —C₃H₇-n H —CH₃ 4-Cl 1 —C₂H₅ H —CH₃ 2,4-Cl₂ 1 —C₂H₅ H —CH₃ 4-F 1 —C₂H₅ H —CH₃ 4-Br 1 —C₂H₅ H —CH₃ 4-NO₂ 1 —C₂H₅ H —CH₃ 4-C₄H₉-t 1 —C₃H₇-i H —CH₃ 4-Cl 1 —C₅H₁₁-n H —CH₃ 4-Cl 1 —CH₃ —CH₃ —CH₃ 4-CN 1 —CH₃ —CH₃ —CH₃ 4-C₄H₉-t 1 —C₄H₉-n H —CH₃ 4-Cl 1 —CH₃ —CH₃ —CH₃ 4-Cl 1 —CH₃ —CH₃ —OCH₃ 4-Cl 1 —C₄H₉-i H —CH₃ 4-Cl 1 —CH₃ —C₂H₅ —CH₃ 4-Cl 1 —CH₃ —CH₃ —OCH₃ 4-Cl 1 —CH₃ —CH₃ —OCH₃ 4-Br 1 —CH₃ —CH₃ —OCH₃ 4-F 1 —CH₃ —CH₃ —OCH₃ 2,4-Cl₂ 1 —CH₃ H —OCH₃ 4-Cl 1 —CH₃ —CH₃ —OCH₃ — 1 —CH₃ —CH₃ —OCH₃ 4-CH₃ 1 —CH₃ —CH₃ —OCH₃ 2-F, 4-Cl 1 —C₂H₅ H —OCH₃ 4-Cl 1 —C₂H₅ —C₂H₅ —OCH₃ 4-Cl 1 —C₃H₇-n H —OCH₃ 4-Cl 1 —C₂H₅ H —OCH₃ 2,4-Cl₂ 1 —C₂H₅ H —OCH₃ 4-F 1 —C₂H₅ H —OCH₃ 4-Br 1 —C₂H₅ H —OCH₃ 4-NO₂ 1 —C₂H₅ H —OCH₃ 4-C₄H₉-t 1 —C₃H₇-i H —OCH₃ 4-Cl 1 —C₅H₁₁-n H —OCH₃ 4-Cl 1 —CH₃ —CH₃ —OCH₃ 4-CN 1 —CH₃ —CH₃ —OCH₃ 4-C₄H₉-t 1 —C₄H₉-n H —OCH₃ 4-Cl 1 —C₄H₉-i H —OCH₃ 4-Cl 1 —CH₃ —C₂H₅ —OCH₃ 4-Cl 1 —CH₃ —CH₃ —CH₃ 4-OCH₃ 1 —CH₃ —CH₃ —CH₃ 2-OCH₃ 1 —CH₃ —CH₃ —CH₃ 2-CF₃ 1 —CH₃ —CH₃ —CH₃ 4-CF₃ 1 —CH₃ —CH₃ —CH₃ 2-OCF₃ 1 —CH₃ —CH₃ —CH₃ 2-OCHF₂ 1 —CH₃ —CH₃ —CH₃ 4-OCF₃ 1 —CH₃ —CH₃ —OCH₃ 4-OCH₃ 1 —CH₃ —CH₃ —OCH₃ 2-OCH₃ 1 —CH₃ —CH₃ —OCH₃ 2-CF₃ 1 —CH₃ —CH₃ —OCH₃ 4-CF₃ 1 —CH₃ —CH₃ —OCH₃ 2-OCF₃ 1 —CH₃ —CH₃ —OCH₃ 2-OCHF₂ 1 —CH₃ —CH₃ —OCH₃ 4-OCF₃ 1 —CH₃ —CH₃ —CH₃ 2-Cl 0 —CH₃ —CH₃ —CH₃ 2,3-Cl₂ 0 —CH₃ —CH₃ —CH₃ 2-Cl 1 —CH₃ —CH₃ —CH₃ 4-Cl 0

TABLE 5 (If)

R¹⁰ R

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃ —C₄H₉-n —CH₃ —C(CH₃)₃ —CH₃ —CH(CH₃)₂ —CH₃

—CH₃

—CH₃ —CH₂—CH(CH₃)₂ —CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—CH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃ —C₄H₉-n —OCH₃ —C(CH₃)₃ —OCH₃ —CH(CH₃)₂ —OCH₃

—OCH₃

—OCH₃ —CH₂—CH(CH₃)₂ —OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—OCH₃

—CH₃

—OCH₃

—NH—CH₃

TABLE 6 (Ig)

X³ _(q) Y¹ R¹¹ R 4-Cl CH₂ H —CH₃ 4-CF₃ CH₂ H —CH₃ 4-OCF₃ CH₂ H —CH₃ 2,4-Cl₂ CH₂ H —CH₃ 4-CH₃ CH₂ H —CH₃ 2-Cl CH₂ H —CH₃ 2-F CH₂ H —CH₃ 4-F CH₂ H —CH₃ 2-OCHF₂ CH₂ H —CH₃ 4-Cl O H —CH₃ 4-CF₃ O H —CH₃ 4-OCF₃ O H —CH₃ 2,4-Cl₂ O H —CH₃ 4-CH₃ O H —CH₃ 2-Cl O H —CH₃ 2-F O H —CH₃ 4-F O H —CH₃ 2-OCHF₂ O H —CH₃ 4-Cl — H —CH₃ 4-CF₃ — H —CH₃ 4-OCF₃ — H —CH₃ 2,4-Cl₂ — H —CH₃ 4-CH₃ — H —CH₃ 2-Cl — H —CH₃ 2-F — H —CH₃ 4-F — H —CH₃ 2-OCHF₂ — H —CH₃ 4-Cl CH₂ —CH₃ —CH₃ 4-CF₃ CH₂ —CH₃ —CH₃ 4-OCF₃ CH₂ —CH₃ —CH₃ 2,4-Cl₂ CH₂ —CH₃ —CH₃ 4-CH₃ CH₂ —CH₃ —CH₃ 2-Cl CH₂ —CH₃ —CH₃ 2-F CH₂ —CH₃ —CH₃ 4-F CH₂ —CH₃ —CH₃ 2-OCHF₂ CH₂ —CH₃ —CH₃ 4-Cl O —CH₃ —CH₃ 4-CF₃ O —CH₃ —CH₃ 2,4-Cl₂ O —CH₃ —CH₃ 4-OCF₃ O —CH₃ —CH₃ 2-F O —CH₃ —CH₃ 2-OCHF₂ O —CH₃ —CH₃ 4-Cl — —CH₃ —CH₃ 4-CF₃ — —CH₃ —CH₃ 2,4-Cl₂ — —CH₃ —CH₃ 4-OCF₃ — —CH₃ —CH₃ 2-F — —CH₃ —CH₃ 2-OCHF₂ — —CH₃ —CH₃ 4-Cl CH₂ C₄H₉-n —CH₃ 2,4-Cl₂ CH₂ —CH(CH₃)₂ —CH₃ 4-OCF₃ CH₂ —C(CH₃)₃ —CH₃ 4-Cl CH₂

—CH₃ 4-Cl CH₂

—CH₃ 4-Cl CH₂

—CH₃ 4-Cl CH₂

—CH₃ 2,4,6-Cl₃ CH₂ —CH₃ —CH₃

CH₂ —CH₃ —CH₃

CH₂ —CH₃ —CH₃ 4-Cl CH₂ H —OCH₃ 4-CF₃ CH₂ H —OCH₃ 4-OCF₃ CH₂ H —OCH₃ 2,4-Cl₂ CH₂ H —OCH₃ 4-CH₃ CH₂ H —OCH₃ 2-Cl CH₂ H —OCH₃ 2-F CH₂ H —OCH₃ 4-F CH₂ H —OCH₃ 2-OCHF₂ CH₂ H —OCH₃ 4-Cl O H —OCH₃ 4-CF₃ O H —OCH₃ 4-OCF₃ O H —OCH₃ 2,4-Cl₂ O H —OCH₃ 4-CH₃ O H —OCH₃ 2-Cl O H —OCH₃ 2-F O H —OCH₃ 4-F O H —OCH₃ 2-OCHF₂ O H —OCH₃ 4-Cl — H —OCH₃ 4-CF₃ — H —OCH₃ 4-OCF₃ — H —OCH₃ 2,4-Cl₂ — H —OCH₃ 4-CH₃ — H —OCH₃ 2-Cl — H —OCH₃ 2-F — H —OCH₃ 4-F — H —OCH₃ 2-OCHF₂ — H —OCH₃ 4-Cl CH₂ —CH₃ —OCH₃ 4-CF₃ CH₂ —CH₃ —OCH₃ 4-OCF₃ CH₂ —CH₃ —OCH₃ 2,4-Cl₂ CH₂ —CH₃ —OCH₃ 4-CH₃ CH₂ —CH₃ —OCH₃ 2-Cl CH₂ —CH₃ —OCH₃ 2-F CH₂ —CH₃ —OCH₃ 4-F CH₂ —CH₃ —OCH₃ 2-OCHF₂ CH₂ —CH₃ —OCH₃ 4-Cl O —CH₃ —OCH₃ 4-CF₃ O —CH₃ —OCH₃ 2,4-Cl₂ O —CH₃ —OCH₃ 4-OCF₃ O —CH₃ —OCH₃ 2-F O —CH₃ —OCH₃ 2-OCHF₂ O —CH₃ —OCH₃ 4-Cl — —CH₃ —OCH₃ 4-CF₃ — —CH₃ —OCH₃ 2,4-Cl₂ — —CH₃ —OCH₃ 4-OCF₃ — —CH₃ —OCH₃ 2-F — —CH₃ —OCH₃ 2-OCHF₂ — —CH₃ —OCH₃ 4-Cl CH₂ —C₄H₉-n —OCH₃ 2,4-Cl₂ CH₂ —CH(CH₃)₂ —OCH₃ 4-OCF₃ CH₂ —C(CH₃)₃ —OCH₃ 4-Cl CH₂

—OCH₃ 4-Cl CH₂

—OCH₃ 4-Cl CH₂

—OCH₃ 4-Cl CH₂

—OCH₃ 2,4,6-Cl₃ CH₂ —CH₃ —OCH₃

CH₂ —CH₃ —OCH₃

—CH₂ —CH₃ —OCH₃ 4-OCF₃ CH₂ —CH₃ —OCH₃

TABLE 7 (Ih)

X⁴ _(f) R¹² R Y² 2,4-Cl₂

—CH₃ O 4-Cl

—CH₃ O 4-Br —C(CH₃)₃ —CH₃ O — —C(CH₃)₃ —CH₃ O 4-C(CH₃)₃ —C(CH₃)₃ —CH₃ O 2-Cl —C(CH₃)₃ —CH₃ O 3-Cl —C(CH₃)₃ —CH₃ O 4-F —C(CH₃)₃ —CH₃ O

—C(CH₃)₃ —CH₃ O

—C(CH₃)₃ —CH₃ O 2,4-Cl₂ —C(CH₃)₃ —CH₃ O 2-CH₃, 4-Cl —C(CH₃)₃ —CH₃ O

—C(CH₃)₃ —OCH₃ O 2,4-Cl₂ —C(CH₃)₃ —OCH₃ O 2-CH₃, 4-Cl —C(CH₃)₃ —OCH₃ O 3,4-(CH₃)₂ —C(CH₃)₃ —OCH₃ O 2,4,5-Cl₃ —C(CH₃)₃ —OCH₃ O 4-Cl —CH₃ —OCH₃ O 4-Cl

—OCH₃ O 4-CF₃ —C(CH₃₎ —OCH₃ O 4-OCF₃ —C(CH₃₎ —OCH₃ O 2-OCHF₂ —C(CH₃₎ —OCH₃ O 4-OCH₃ —C(CH₃)₃ —OCH₃ O 4-Cl

—CH₃ O 4-Cl

—CH₃ O 4-Cl

—OCH₃ O 3,4-(CH₃)₂ —C(CH₃)₃ —CH₃ O 2,4,5-Cl₃ —C(CH₃)₃ —CH₃ O 4-Cl —CH₃ —CH₃ O 4-Cl

—CH₃ O 4-CF₃ —C(CH₃)₃ —CH₃ O 4-OCF₃ —C(CH₃)₃ —CH₃ O 2-OCHF₂ —C(CH₃)₃ —CH₃ O 4-OCH₃ —C(CH₃)₃ —CH₃ O 2,4-Cl₂

—OCH₃ O 4-Cl

—OCH₃ O 4-Br —C(CH₃)₃ —OCH₃ O — —C(CH₃)₃ —OCH₃ O 4-C(CH₃)₃ —C(CH₃)₃ —OCH₃ O 2-Cl —C(CH₃)₃ —OCH₃ O 3-Cl —C(CH₃)₃ —OCH₃ O 4-F —C(CH₃)₃ —OCH₃ O

—C(CH₃)₃ —OCH₃ O 4-Cl

—OCH₃ O 2,4-Cl₂

—CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Br —C(CH₃)₃ —CH₃ CH₂ — —C(CH₃)₃ —CH₃ CH₂ 4-C(CH₃)₃ —C(CH₃)₃ —CH₃ CH₂ 2-Cl —C(CH₃)₃ —CH₃ CH₂ 3-Cl —C(CH₃)₃ —CH₃ CH₂ 4-F —C(CH₃)₃ —CH₃ CH₂

—C(CH₃)₃ —CH₃ CH₂

—C(CH₃)₃ —CH₃ CH₂ 2,4-Cl₂ —C(CH₃)₃ —CH₃ CH₂ 2-CH₃, 4-Cl —C(CH₃)₃ —CH₃ CH₂ 3,4-(CH₃)₂ —C(CH₃)₃ —CH₃ CH₂ 2,4,5-Cl₃ —C(CH₃)₃ —CH₃ CH₂ 4-Cl —CH₃ —CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-CF₃ —C(CH₃)₃ —CH₃ CH₂ 4-OCF₃ —C(CH₃)₃ —CH₃ CH₂ 2-OCHF₂ —C(CH₃)₃ —CH₃ CH₂ 4-OCH₃ —C(CH₃)₃ —CH₃ CH₂ 2,4-Cl₂

—OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Br —C(CH₃)₃ —OCH₃ CH₂ — —C(CH₃)₃ —OCH₃ CH₂ 4-C(CH₃)₃ —C(CH₃)₃ —OCH₃ CH₂ 2-Cl —C(CH₃)₃ —OCH₃ CH₂ 3-Cl —C(CH₃)₃ —OCH₃ CH₂ 4-F —C(CH₃)₃ —OCH₃ CH₂

—C(CH₃)₃ —OCH₃ CH₂

—C(CH₃)₃ —OCH₃ CH₂ 2,4-Cl₂ —C(CH₃)₃ —OCH₃ CH₂ 2-CH₃, 4-Cl —C(CH₃)₃ —OCH₃ CH₂ 3,4-(CH₃)₂ —C(CH₃)₃ —OCH₃ CH₂ 2,4,5-Cl₃ —C(CH₃)₃ —OCH₃ CH₂ 4-Cl —C(CH₃)₃ —OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-CF₃ —C(CH₃)₃ —OCH₃ CH₂ 4-OCF₃ —C(CH₃)₃ —OCH₃ CH₂ 2-OCHF₂ —C(CH₃)₃ —OCH₃ CH₂ 4-OCH₃ —C(CH₃)₃ —OCH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Cl —C(CH₃)₃ —CH₃ O 4-Cl —C(CH₃)₃ —OCH₃ O 4-Cl —C(CH₃)₃ —NH—CH₃ O

TABLE 8 (Ii)

X⁵ _(s) A R 2,4-Cl₂ —(CH₂)₃— —CH₃ 2,4-Cl₂ —(CH₂)₂— —CH₃ 4-Cl

—CH₃ 4-CF₃

—CH₃ 2-Cl, —CH₂—CH₂— —CH₃

2-Cl,

—CH₃

4-F

—CH₃ 4-OCF₃

—CH₃ 2,4-F₂

—CH₃ 2-OCHF₂

—CH₃ 2-Cl, —(CH₂)₃— —CH₃

2,4,6-Cl₃

—CH₃ —

—CH₃ 2,4-F₂

—CH₃ 2-Cl,

—CH₃

2,4-Cl₂

—CH₃ 2-Cl,

—CH₃

2,4-Cl₂

—CH₃ 2-Cl

—CH₃

2,4-Cl₂

—CH₃ 2,4-Cl₂ —(CH₂)₃— —OCH₃ 2,4-Cl₂ —(CH₂)₂— —OCH₃ 4-Cl

—OCH₃ 4-CF₃

—OCH₃ 2-Cl, —CH₂—CH₂— —OCH₃

2-Cl,

—OCH₃

4-F

—OCH₃ 4-OCF₃

—OCH₃ 2,4-F₂

—OCH₃ 2-OCHF₂

—OCH₃ 2-Cl, —(CH₂)₃— —OCH₃

2,4,6-Cl₃

—OCH₃ —

—OCH₃ 2,4-F₂

—OCH₃ 2-Cl,

—OCH₃

2,4-Cl₂

—OCH₃ 2-Cl,

—OCH₃

2,4-Cl₂

—OCH₃ 2-Cl

—OCH₃

2,4-Cl₂

—OCH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—NH—CH₃

TABLE 9 (1k)

X⁶ _(t) R¹³ R 2,4-Cl₂ —CH₃ —CH₃ 2,4-Cl₂ —C₂H₅ —CH₃ 2,4-Cl₂ —CH(CH₃)₂ —CH₃ 4-Cl —C₃H₇-n —CH₃ 2,4-Cl₂ —C₄H₉-n —CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂ —C(CH₃)₃ —CH₃ 2-Cl —C₃H₇-n —CH₃ 2-OCF₃ —C₃H₇-n —CH₃ 4-CF₃ —C₃H₇-n —CH₃ 4-CH₃ —C₃H₇-n —CH₃ 2,4,6-Cl₃ —C₃H₇-n —CH₃ 2,4-Cl₂

—CH₃ 4-F —C₃H₇-n —CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂

—CH₃ 2,4-Cl₂ —CH₂—O—CF₂—CHF₂ —CH₃ 2,4-Cl₂ —CH₂—O—CF₂—CH₃ —CH₃ 4-Cl —CH₂—O—CF₂—CHF₂ —CH₃ 2,4-Cl₂ —CH₂—O—CF₃ —CH₃ 4-F —CH₂—O—CF₂—CHF₂ —CH₃ 2-Cl —CH₂—O—CF₂—CHF₂ —CH₃ 2,4-Cl₂ —CH₃ —OCH₃ 2,4-Cl₂ —C₂H₅ —OCH₃ 2,4-Cl₂ —CH(CH₃)₂ —OCH₃ 4-Cl —C₃H₇-n —OCH₃ 2,4-Cl₂ —C₄H₉-n —OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂ —C(CH₃)₃ —OCH₃ 2-Cl —C₃H₇-n —OCH₃ 2-OCF₃ —C₃H₇-n —OCH₃ 4-CF₃ —C₃H₇-n —OCH₃ 4-CH₃ —C₃H₇-n —OCH₃ 2,4,6-Cl₃ —C₃H₇-n —OCH₃ 2,4-Cl₂

—OCH₃ 4-F —C₃H₇-n —OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂

—OCH₃ 2,4-Cl₂ —CH₂—O—CF₂—CHF₂ —OCH₃ 2,4-Cl₂ —CH₂—O—CF₂—CH₃ —OCH₃ 4-Cl —CH₂—O—CF₂—CHF₂ —OCH₃ 2,4-Cl₂ —CH₂—O—CF₃ —OCH₃ 4-F —CH₂O—CF₂—CHF₂ —OCH₃ 2-Cl —CH₂—O—CF₂—CHF₂ —OCH₃ 2,4-Cl₂ —CH₂—CF₃ —CH₃ 2,4-Cl₂ —CF₂—CF₃ —CH₃ 2,4-Cl₂ —C₃H₇-n —CH₃ 2,4-Cl₂ —C₃H₇-n —OCH₃ 2,4-Cl₂ —C₃H₇-n —NH—CH₃

TABLE 10 (1m)

X⁷ _(u) R¹⁴ R Y³ 2,4-Cl₂

—CH₃ O 4-Cl

—CH₃ O 4-Br —C(CH₃)₃ —CH₃ O — —C(CH₃)₃ —CH₃ O 4-C(CH₃)₃ —C(CH₃)₃ —CH₃ O 2-Cl —C(CH₃)₃ —CH₃ O 3-Cl —C(CH₃)₃ —CH₃ O 4-F —C(CH₃)₃ —CH₃ O

—C(CH₃)₃ —CH₃ O

—C(CH₃)₃ —CH₃ O 2,4-Cl₂ —C(CH₃)₃ —CH₃ O 2-CH₃, 4-Cl —C(CH₃)₃ —CH₃ O 3,4-(CH₃)₂ —C(CH₃)₃ —CH₃ O 2,4,5-Cl₃ —C(CH₃)₃ —CH₃ O 4-Cl —CH₃ —CH₃ O 4-Cl

—CH₃ O 4-CF₃ —C(CH₃)₃ —CH₃ O 4-OCF₃ —C(CH₃)₃ —CH₃ O 2-OCHF₂ —C(CH₃)₃ —CH₃ O 4-OCH₃ —C(CH₃)₃ —CH₃ O 2,4-Cl₂

—OCH₃ O 4-Cl

—OCH₃ O 4-Br —C(CH₃)₃ —OCH₃ O — —C(CH₃)₃ —OCH₃ O 4-C(CH₃)₃ —C(CH₃)₃ —OCH₃ O 2-Cl —C(CH₃)₃ —OCH₃ O 3-Cl —C(CH₃)₃ —OCH₃ O 4-F —C(CH₃)₃ —OCH₃ O

—C(CH₃)₃ —OCH₃ O

—C(CH₃)₃ —OCH₃ O 2,4-Cl₂ —C(CH₃)₃ —OCH₃ O 2-CH₃, 4-Cl —C(CH₃)₃ —OCH₃ O 3,4-(CH₃)₂ —C(CH₃)₃ —OCH₃ O 2,4,5-Cl₃ —C(CH₃)₃ —OCH₃ O 4-Cl —CH₃ —OCH₃ O 4-Cl

—OCH₃ O 4-CF₃ —C(CH₃)₃ —OCH₃ O 4-OCF₃ —C(CH₃)₃ —OCH₃ O 2-OCHF₂ —C(CH₃)₃ —OCH₃ O 4-OCH₃ —C(CH₃)₃ —OCH₃ O 4-Cl

—CH₃ O 4-Cl

—CH₃ O 4-Cl

—OCH₃ O 4-Cl

—OCH₃ O 2,4-Cl₂

—CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Br —C(CH₃)₃ —CH₃ CH₂ — —C(CH₃)₃ —CH₃ CH₂ 4-C(CH₃)₃ —C(CH₃)₃ —CH₃ CH₂ 2-Cl —C(CH₃)₃ —CH₃ CH₂ 3-Cl —C(CH₃)₃ —CH₃ CH₂ 4-F —C(CH₃)₃ —CH₃ CH₂

—C(CH₃)₃ —CH₃ CH₂

—C(CH₃)₃ —CH₃ CH₂ 2,4-Cl₂ —C(CH₃)₃ —CH₃ CH₂ 2-CH₃, 4-Cl —C(CH₃)₃ —CH₃ CH₂ 3,4-(CH₃)₂ —C(CH₃)₃ —CH₃ CH₂ 2,4,5-Cl₃ —C(CH₃)₃ —CH₃ CH₂ 4-Cl —CH₃ —CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-CF₃ —C(CH₃)₃ —CH₃ CH₂ 4-OCF₃ —C(CH₃)₃ —CH₃ CH₂ 2-OCHF₂ —C(CH₃)₃ —CH₃ CH₂ 4-OCH₃ —C(CH₃)₃ —CH₃ CH₂ 2,4-Cl₂

—OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Br —C(CH₃)₃ —OCH₃ CH₂ — —C(CH₃)₃ —OCH₃ CH₂ 4—C(CH₃)₃ —C(CH₃)₃ —OCH₃ CH₂ 2-Cl —C(CH₃)₃ —OCH₃ CH₂ 3-Cl —C(CH₃)₃ —OCH₃ CH₂ 4-F —C(CH₃)₃ —OCH₃ CH₂

—C(CH₃)₃ —OCH₃ CH₂

—C(CH₃)₃ —OCH₃ CH₂ 2,4-Cl₂ —C(CH₃)₃ —OCH₃ CH₂ 2-CH₃, 4-Cl —C(CH₃)₃ —OCH₃ CH₂ 3,4-(CH₃)₂ —C(CH₃)₃ —OCH₃ CH₂ 2,4,5-Cl₃ —C(CH₃)₃ —OCH₃ CH₂ 4-Cl —CH₃ —OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-CF₃ —C(CH₃)₃ —OCH₃ CH₂ 4-OCF₃ —C(CH₃)₃ —OCH₃ CH₂ 2-OCHF₂ —C(CH₃)₃ —OCH₃ CH₂ 4-OCH₃ —C(CH₃)₃ —OCH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Cl

—CH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Cl

—OCH₃ CH₂ 4-Cl —C(CH₃)₃ —CH₃ O 4-Cl —C(CH₃)₃ —OCH₃ O 4-Cl —C(CH₃)₃ —NH—CH₃ O

TABLE 11 (1n)

X⁸ _(v) R¹⁵ R Cl —C₄H₉-n —CH₃ 2-Cl —C₄H₉-n —CH₃ 2,4-Cl₂ —C₄H₉-n —CH₃ 4-Br —C₄H₉-n —CH₃ 4-F —C₄H₉-n —CH₃ 4-C(CH₃)₃ —C₄H₉-n —CH₃

—C₄H₉-n —CH₃ 4-Cl —C(CH₃)₃ —CH₃ 2-Cl —C(CH₃)₃ —CH₃ 2,4-Cl₂ —C(CH₃)₃ —CH₃ 2,4,6-Cl₃ —C(CH₃)₃ —CH₃ 4-CF₃ —C(CH₃)₃ —CH₃ 2-OCHF₂ —C(CH₃)₃ —CH₃ 4-Cl

—CH₃ 4-Cl

—CH₃ 4-Cl

—CH₃ 4-Cl

—CH₃ 4-Cl

—CH₃ 4-Cl

—CH₃ —

—CH₃ 4-Cl —C₄H₉-n —OCH₃ 2-Cl —C₄H₉-n —OCH₃ 2,4-Cl₂ —C₄H₉-n —OCH₃ 4-Br —C₄H₉-n —OCH₃ 4-F —C₄H₉-n —OCH₃ 4-C(CH₃)₃ —C₄H₉-n —OCH₃

—C₄H₉-n —OCH₃ 4-Cl —C(CH₃)₃ —OCH₃ 2-Cl —C(CH₃)₃ —OCH₃ 2,4-Cl₂ —C(CH₃)₃ —OCH₃ 2,4,6-Cl₃ —C(CH₃)₃ —OCH₃ 4-CF₃ —C(CH₃)₃ —OCH₃ 2-OCHF₂ —C(CH₃)₃ —OCH₃ 4-Cl

—OCH₃ 4-Cl

—OCH₃ 4-Cl

—OCH₃ 4-Cl

—OCH₃ 4-Cl

—OCH₃ 4-Cl

—OCH₃ —

—OCH₃ —

—OCH₃ —

—CH₃ —

—NH—CH₃

Using 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol as starting material and acetyl chloride as reaction component, the course of the process according to the invention (variant a) can be illustrated by the equation below.

Using 2-(1-chloro-cyclopropyl)-1-(2-chioro-phenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol as starting material and methyl chloroformate as reaction component, the course of the process according to the invention (variant b) can be illustrated by the equation below.

Using 2-(1-chloro-cyclopropyl)-1-(2-chloro-phenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol as starting material and methyl isocyanate as reaction component, the course of the process according to the invention (variant c) can be illustrated by the equation below.

The formula (II) provides a general definition of the mercapto-triazoles required as starting materials for carrying out the process according to the invention. In this formula. R¹ preferably has those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this radical.

The mercapto-triazoles of the formula (II) have hitherto not been disclosed. They can be prepared by reacting triazoles of the formula

in which

R¹ is as defined above

 either

α) successively with strong bases and sulphur in the presence of a diluent, followed by hydrolysis with water, if appropriate in the presence of an acid,

 or

β) with sulphur in the presence of a high-boiling diluent, followed, if appropriate, by treatment with water and, if appropriate, with acid.

The formula (VI) provides a general definition of the triazoles required as starting materials for carrying out the process for preparing mercapto-triazoles of the formula (II).In this formula. R¹ preferably has those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for this radical.

The triazoles of the formula (VI) are known or can be prepared by known methods (cf.

EP-A 0 015 756, EP-A 0 040 345, EP-A 0 052 424, EP-A 0 061 835, EP-A 0 297 345, EP-A 0 094 564, EP-A 0 196 038, EP-A 0 267 778, EP-A 0 378 953, EP-A 0 044 605, EP-A 0 069 442, EP-A 0 055 833, EP-A 0 301 393, DE-A 2 324 010, DE-A 2 737 489, DE-A 2 551 560, DE-A 2 065 485, DE-A 2 735 872, EP-A 0 234 242, DE-A 2 201 063, EP-A 0 145 294, and DE-A 2 721 786

Suitable bases for carrying out the above process (α) for preparing mercaptotriazoles of the formula (II) are all strong alkali metal bases which are customary for such reactions. Preference is given to using n-butyl-lithium, lithium diisopropyl-amide, sodium hydride, sodium amide and also potassium tert-butoxide in a mixture with tetramethylethylene-diamine (=TMEDA).

Suitable diluents for carrying out the above process (α) for preparing mercaptotriazoles of the formula (II) are all inert organic solvents which are customary for such reactions. Preference is given to using ethers, such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, furthermore liquid ammonia or else strongly polar solvents, such as dimethyl sulphoxide.

Both when carrying out the above process (α) and also the process (β) sulphur is preferably employed in the form of a powder.

When carrying out the above process (α), water, if appropriate in the presence of an acid, is employed for hydrolysis. Suitable acids here are all inorganic or organic acids which are customary for such reactions. Preference is given to using acetic acid, dilute sulphuric acid and dilute hydrochloric acid. However, it is also possible to carry out the hydrolysis using aqueous ammonium chloride solution.

When carrvini out the above process (α), the reaction temperatures can be varied within a certain range. In general, the process is carried out at temperatures between −70° C. and +20° C. preferably between −70° C. and 0° C.

The above processes (α) and (β) are generally carried out under atmospheric pressure.

However, it is also possible to operate under elevated or reduced pressure. Thus, in particular when carrying out the process (β), operation under elevated pressure is possible.

When carrying out the above process (α). generally 2 to 3 equivalents. preferably 2.0 to 2.5 equivalents, of strong base and subsequently an equivalent amount or else an excess of sulphur are employed per mole of triazole of the formula (VI). The reaction can be carried out under an atmosphere of protective gas, for example under nitrogen or argon. Work-up is carried out by customary methods. In general, the reaction mixture is extracted with an organic solvent which is only sparingly soluble in water, the combined organic phases are dried and concentrated and the residue that remains is, if appropriate, purified by recrystallization and/or chromatography.

Suitable diluents for carrying out the above process (β) are all high-boiling organic solvents which are customary for such reactions. Preference is given to using amides, such as dimethylformamide and dimethylacetamide, furthermore heterocyclic compounds, such as N-methyl-pyrrolidone, and also ethers, such as diphenyl ether.

When carrying out the above process (β), a treatment with water and, if appropriate, with acid, can be carried out, if appropriate, after the reaction. This treatment is carried out like the hydrolysis in the practice of the process (α).

When carrying out the above process (β), the reaction temperatures can also be varied within a relatively large range. In general, the reaction is carried out at temperatures between 150° C. and 300° C., preferably between 180° C. and 250° C.

When carrying out the above process (β), generally 1 to 5 mol, preferably 1.5 to 3 mol, of sulphur are employed per mole of triazole of the formula (VI). Work-up is carried out by customary methods. In general, the reaction mixture is extracted with an organic solvent which is only sparingly soluble in water, the combined organic phases are dried and concentrated and the residue that remains is, if appropriate, freed of any impurities that may be present using customary methods, such as recrystallization or chromatography.

The formula (III) provides a general definition of the acyl halides required as reaction components for carrying out variant (a) of the process according to the invention. In this formula, R¹⁶ preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms or represents phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the croup consisting of halogen and alkyl having 1 to 4 carbon atoms, Hal also preferably represents chlorine or bromine.

R¹⁶ particularly preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straighit-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl or represents phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl. Hal particularly preferably represents chlorine.

The acyl halides of the formula (III) are known or can be prepared by known methods.

Suitable acid binders for carrying out variant (a) of the process according to the invention are all customary inorganic or organic bases. Preference is given to using alkali metal hvdrides, such as lithium hydride or sodium hydride, furthermore alkaline earth metal hydroxides or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or else ammonium hydroxide, alkali metal carbonates, such as sodium carbonat,. potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal acetates or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, and also tertiar amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-metliylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU),

Suitable diluents for carrying out variant (a) of the process according to the invention are all customary inert organic solvents. Preference is given to using aromatic hydrocarbons, such as toluene, xylene or decalin, furthermore halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichiloroethane, moreover ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane or tetrahydrofuran, and furthermore nitrites, such as acetonitrile, propionitrile, n- or isobutyronitrile.

When carrying out variant (a) of the process according to the invention, the reaction temperatures can be varied within a relatively wide range, In general, the process is carried out at temperatures between −20° C. and +120° C., preferably at temperatures between 0° C. and +100° C.

Both variant (a) and variants (b) or (c) of the process according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure,

When carrving out variant (a) of the process according to the invention, generally 1 to 3 mol of acyl halide of the formula (III) and an equivalent amount or else an excess of acid binder are employed per mole of mercapto-triazole of the formula (II). Work-up is carried out by customary methods. In general, the reaction mixture is, if appropriate after prior addition of a little alcohol, concentrated under reduced pressure, the residue that remains is extracted with an organic solvent which is only sparingly miscible with water and the combined organic phases are concentrated under reduced pressure. The product that is obtained can, if appropriate, be freed of any impurities that may still be present using customary methods, for example recrystallization or chromatography,

The formula (IV) provides a general definition of the halogenoformates required as reaction components for carrying out variant (b) of the process according to the invention, In this formula, R¹⁷ preferably represents straight-chain or branched alkyl having 1 to 12 carbon atoms, Hal¹ also preferably represents chlorine or bromine,

R¹⁷ particularly preferably represents straight-chain or branched alkyl having 1 to 10 carbon atoms, Hal¹ particularly preferably represents chlorine.

The halogenoformates of the formula (IV) are known or can be prepared by known methods.

Suitable acid binders for carrying out variant (b) of the process according to the invention are all inorganic or organic bases which are customary for such reactions. Preference is given to using those acid binders which have already been mentioned in connection with the description of process variant (a) as being preferred.

Suitable diluents for carrying out variant (b) of the process according to the invention are again all inert organic solvents which are customary for such reactions. Preference is given to using those solvents which have already been mentioned in connection with the description of process variant (a) as being preferred.

When carrying out variant (b) of the process according to the invention, the reaction temperatures can again be varied within a certain range. In general, the reaction is carried out at temperatures between −20° C. and +100° C., preferably between −10° C. and +80° C.

When carrving out variant (b) of the process according to the invention, generally 1 to 2 mol of halogenoformate of the formula (IV) and an equivalent amount or else an excess of acid binder are employed per mole of mercapto-triazole of the formula (II). Work-up is carried out by customary methods. In general, the reaction mixture is diluted with an organic solvent which is only sparingly miscible with water and then extracted with weakly basic aqueous solution, and the organic phase is then dried and concentrated under reduced pressure. The product that is obtained can, if appropriate, be freed of any impurities that may still be present using customary methods, for example recrystallization or chromatography.

The formula (V) provides a general definition of the isocyanates required as reaction components for carrying out variant (c) of the process according to the invention. In this formula, R¹⁸ preferably represents straight-chain or branched alkyl having 1 to 14 carbon atoms or represents phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms.

R¹⁸ particularly preferably represents straight-chain or branched alkyl having 1 to 12 carbon atoms or represents phenyl which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.

The isocyanates of the formula (V) are known or can be prepared by known methods.

Suitable catalysts for carrying out variant (c) of the process according to the invention are all reaction promoters which are customary for such reactions. Preference is given to using amines, such as triethylamine, pyridine, dimethylaminopyridine and diazabicyclo-undecene (DBU).

Suitable diluents for carrying out variant (c) of the process according to the invention are again all inert organic solvents which are customary for such reactions. Preference is given to using those solvents which have already been mentioned in connection with the description of process variant (a) as being preferred.

When carrying out variant (c) of the process according to the invention, the reaction temperatures can again be varied within a certain range. In general, the reaction is carried out at temperatures between −20° C. and +100° C., preferably between 0° C. and +80° C.

When carrying out variant (c) of the process according to the invention, generally 1 to 1.5 mol of isocyanate of the formula (V) and a small amount of catalyst are employed per mole of mercapto-triazole of the formula (II). Work-up is carried out by customary methods. In general, the reaction mixture is concentrated under reduced pressure and the product that remains is freed of any impurities that may still be present using customary methods, for example recrystallization or chromatography,

The acyl-mercapto-triazolyl derivatives of the formula (I) which can be obtained by the process according to the invention can be converted into acid addition salts or metal salt complexes.

Suitable acids for the preparation of acid addition salts of the compounds of the formula (I) are preferably those which have already been mentioned in connection with the description of the acid addition salts according to the invention as being preferred acids.

The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by filtering off, and, if appropriate, purified by washing with an inert organic solvent,

Suitable salts for the preparation of metal salt complexes of the compounds of the formula (I) are preferably those of metals which have already been mentioned in connection with the description of the metal salt complexes according to the invention as being preferred metal salts.

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compounds of the formula (I), Metal salt complexes can be isolated in a known manner, for example by filtering off, and, if appropriate, purified by recrystallization.

The active compounds according to the invention have strong microbicidal activity and can be employed for controlling undesirable microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

In crop protection, fungicides are employed for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola;

Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea;

(conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus;

(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae;

Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good tolerance, by plants, of the active compounds, at the concentrations required for controlling plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

The active compounds according to the invention are particularly suitable for controlling Pyricularia oryzae and Pellicularia sasakii on rice, and also for controlling cereal diseases, such as Pseudocercosporella, Erysiphe species and Fusarium species. Furthermore, the substances according to the invention can also be used effectively against Venturia and Sphaerotheca. Additionally, they also have very good in vitro activity.

In materials protection the substances of the invention can be used to protect industrial materials against infestation and destruction by undesirable microorganisms.

The term industrial materials in the present context refers to nonliving materials which have been prepared for use in industry. Examples can be industrial materials which are to be protected by novel active compounds against microbial alteration or destruction, adhesives, sizes, paper and card, textiles, leather, wood, coating compositions and plastics articles, cooling lubricants and other materials which can be infested or decomposed by microorganisms. In the context of the materials to be protected mention may also be made of parts of production plants, for example cooling water circuits, which may be adversely affected by reproduction of microorganisms. Preferred industrial materials in the context of the present invention are adhesives, sizes, papers and cards, leather, wood, coating compositions, cooling lubricants and heat transfer fluids, particularly preferably wood.

Examples of microorganisms which can bring about degradation or an alteration in the industrial materials are bacteria, fungi, yeasts, algae and slime organisms, The active compounds according to the invention preferably act against fungi, especially mould fungi, wood-discolouring and wood-destroying fungi (Basidiomycetes) and also against slime organisms and algae.

By way of example of microorganisms, mention may be made of the following genera:

Altemaria, such as Altemaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and/or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, and also ULV cold-mist and warm-mist formulations.

These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkyliaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powvders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Possible further additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal plithalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0.1 and 95 per cent by wreight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, when used in crop protection, can be used as such or in their formulations as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, for example so as to widen the spectrum of action or to prevent the build up of resistance. In many cases, synergistic effects are obtained, i.e. the efficacy of the mixture is higher than the efficacy of the individual components.

Suitable components for the mixtures are, for example, the following substances:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate; 2-phenyiphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram.

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon,

edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,

nickel dimethyiditihiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tehuconazole, tecloftalam, technazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram

Bactenicides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyidithiocarbamate, kasugamycin, octhilinonie, furanecarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalamn, copper sulphate and other copper preparations.

Insecticides/Acancides/Nematicides:

abamectin. AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben.

cadusafos, carbaryl, carbofuran, carbophelnothioti, carbosulfan, cartap, CGA 157 419. CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlornieplios, chlorpyrifos, chlorpyrifos M, cis-resinethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinani, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furatliiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imnidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenfos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, is also possible.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules, They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation or the active compound itself into the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants, the concentrations of active compound in the use forms can be varied within a relatively large range: they are in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the treatment of seed, amounts of active compound of from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 10 g, are generally required.

In the case of the treatment of soil, active-compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, are required at the site of action.

The compositions used for protecting industrial materials comprise the active compounds in an amount of in general from 1 to 95%, preferably from 10 to 75%.

The concentrations in which the novel active compounds are applied depend on the nature and on the incidence of the microorganisms to be controlled and on the composition of tile material to be protected, The optimum amount for use can be determined by means of test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and the spectrum of action of the active compounds to be used in materials protection in accordance with the invention and of the compositions, concentrates or, very generally, formulations which can be prepared therefrom can be increased by adding, if desired, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds to increase the spectrum of action or to achieve particular effects, for example additional protection against insects. These mixtures may possess a broader spectrum of action than the compounds according to the invention.

The preparation and the use of the substances according to the invention are illustrated by the examples below.

PREPARATION EXAMPLES Examnple 1

At room temperature, a mixture of 1.72 g (5 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol in 20 ml of absolute tetrahydrofuran is admixed with stirring with 0.24 g (6 mmol) of sodium hydride (60% strength in paraffin oil) and stirred for 30 minutes, 0.72 ml (10 mmol) of acetyl chloride are then added and the reaction mixture is stirred at room temperature for a further 4 hours. The reaction mixture is then admixed with 1 ml of ethanol and concentrated under reduced pressure. The residue that remains is extracted repeatedly with dichloromethane. The combined organic phases are concentrated under reduced pressure. In this manner, 1.8 g (94% of theory) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-acetylmercapto-1,2,4-triazol-1-yl)-propan-2-ol are obtained in the form of an oil.

¹H NMR spectrum (400 MHz; CDCl₃; TMS): δ=0.8-1.0 (m, 4H); 3.0 (s, 3H); 3.3 (d, 1H); 3.6 (d, 1H); 4.1 (s, OH); 4.6 (d, 1H); 4.75 (d, 1H); 7.2-7.55 (m, 4H); 8.5 (s, 1H) ppm.

Example 2

At room temperature, a solution of 0.63 ml (5 mmol) of 4-chloro-benzo)yl chloride in 5 ml of absolute tetrahydrofuran is added dropwise with stirring to a mixture of 1.72 g (5 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol, 0.69 g (5 mmol) of anhydrous potassium carbonate and 20 ml of absolute tetrahydrofuran. The reaction mixture is stirred at room temperature for a further 20 hours and then filtered off with suction and concentrated under reduced pressure. In this manner, 2.4 g (99% of theory) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-[5-(4-chloro-benzoyl-mercapto)-1,2,4-triazol-1-yl]-propan-2-ol are obtained in the form of an oil.

¹H NMR spectrum (400 MHz; CDCl₃; TMS): δ=0.5-1.0 (m, 4H); 3.15 (d, 1H); 3.7 (d, 1H); 4.1 (d, 1H); 5.05 (d, 1H); 7.2-8.1 (m, 8H); 8.15 (s, 1H) ppm.

The substances listed in the examples below are also prepared by the methods given above.

Example 3

Melting point: 160° C.

Example 4

Oil

¹H NMR spectrum (400 MHz; CDCl₃; TMS); δ=0.5-1.0 (m, 4H), 1.35 (s, 9H), 3.0 (d, 1H), 3.65 (d, 1H), 3.9 (d, 1H) 4.6 (OH), 4.9 (d, 1H), 7.2-7.55 (m, 4H), 8.1 (s, 1H).

Example 5

At temperatures between 0 and 5° C., first a solution of 1.28 ml (6 mmol) of methyl chloroformate in 10 ml of absolute dichloromethane and then 0.84 ml (6 mmol) of triethylamine are added dropwise with stirring to a mixture of 1.72 g (5 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol and 10 ml of absolute dichloromethane. After the addition, the reaction mixture is stirred at room temperature for a further 2 hours and then diluted with dichloromethane and washed with ice-cold aqueous sodium carbonate solution. The organic phase is dried over sodium sulphate and subsequently concentrated under reduced pressure. The 1.7 g of crude product that remain are chromatographed over silica gel using a mixture of petroleum ether/ethyl acetate=1:1. Concentration of the eluate gives 0.7 g (35% of theory) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-methoxycarbonylthio-1,2,4-triazol-1-yl)-propan-2-ol in the form of an oil.

¹H NMR spectrum (200 MHz; CDCl₃; TMS): δ=0.5-1.05 (m, 4H); 2.7 (s, 3H); 3.1 (d, 1H); 3.6 (d, 1H); 3.9 (d, 1H); 4.7 (s, OH); 4.8 (d, 1H); 7.15-7.6 (m, 4H); 7.85 (s, 1H) ppm.

The compounds listed in the examples below are also prepared by the method given in Example 5.

Example 6

Melting point: 86 to 90° C.

Example 7

MS (ci): 500 (M+H⁺).

Example 8

At room temperature, a solution of 0.3 ml (5 mmol) of methyl isocyanate in 5 ml of absolute tetrallydrofuran is added dropwise with stirring to a mixture of 1.72 g (5 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol, 0.1 ml of triethylamine and 20 ml of absolute tetrahydrofuran. After the addition, the reaction mixture is stirred at room temperature for 1 hour and then concentrated under reduced pressure. The crude product that remains is chromatographed over silica gel using a mixture of petroleum ether/ethyl acetate=1:1. Concentration of the eluate gives 1.3 g (65% of theory) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-[5-(N-methyl-carbamoylthio)-1,2,4-triazol-1-yl]-propan-2-ol in the form of an oil.

¹H NMR spectrum (400 MHz; CDCl₃; TMS): δ=0.8-1.0 (m, 4H); 3.05 (d, 3H); 3.2 (d, 1H); 3.6 (d, 1H); 3.7 (s, OH); 4.5 (d, 1H); 4.8 (d, 1H); 7.2-7.55 (m, 4H); 8.6 (s, 1H); 9.9 (s, NH) ppm.

The compounds listed in the examples below are also prepared by the method given in Example 8.

Example 9

Melting point: 125° C.

Example 10

Oil

¹H NMR spectrum (200 MHz; CDCl₃; TMS): δ=0.8-10 (m, (4H), 1.2-1.7 (m, 23H), 3.2 (d, 1H), 3.4 (q, 2H), 3.6 (d, 1H), 3.7 (OH), 4.55 (d, 1H), 4.8 (d, 1H), 7.2-7.55 (m, 4H), 8.1 (s, 1H), 9.9 (NH).

Example 11

¹H NMR spectrum (400 M Hz; CDCl₃; TMS): δ=0.7-1.0 (m, 4H ), 1.3 (d, 6H ), 3.2 (d, 1H), 3.6 (d, 1H), 4.1 (m, 1H), 4.55 (d, 1H), 4.75 (d, 1H), 7.15-7.6 (m, 4H ), 8.6 (s, 1H), 9.9 (NH).

Example 12

Oil

¹H NMR spectrum (400 MHz; CDCl₃; TMS): δ=0.7-1.0 (m, 4H), 3.25 (d, 1H), 3.55 (OH), 3.6 (d, 1H), 4.55 (d, 1H), 4.8 (d, 1H) 7.15-7.6 (m, 8H), 8.7 (s, 1H), 12.2 (NH).

Preparation of Starting Materials Example 13

Variant α:

At −20° C., a mixture of 3.12 g (10 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol and 45 ml of absolute tetrahydrofuran is admixed with 8.4 ml (21 mmol) of n-butyl-lithium in hexane and stirred at 0° C. for 30 minutes. The reaction mixture is subsequently cooled to −70° C., admixed with 0.32 g (10 mmol) of sulphur powder and stirred at −70° C. for 30 minutes. The mixture is warmed to −10° C., admixed with ice-water and adjusted to pH 5 by addition of dilute sulphuric acid, The mixture is extracted repeatedly with ethyl acetate and the combined organic phases are dried over sodium sulphate and concentrated under reduced pressure. In this manner, 3.2 g (93% of theory) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol) are obtained in the form of a solid substance which, after recrystallization, melts at 138-139° C.

Variant β:

With stirring, a mixture of 3.12 g (10 mmol) of 2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, 0.96 g (30 mmol) of sulphur powder and 20 ml of absolute N-methyl-pyrrolidone is heated at 200° C. for 44 hours. The reaction mixture is subsequently concentrated under reduced pressure (0.2 mbar). The resulting crude product (3.1 g) is recrystallized from toluene. In this manner, 0.7 g (20% of theory) of 2-(1-chiloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-yl)-propan-2-ol is obtained in the form of a solid substance of melting point 138-139° C.

Example 14

At −70° C., a mixture of 1.41 g (5 mmol) of 1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentene and 25 ml of absolute tetrahydrofuran is admixed with 4 ml (10 mmol) of n-butyl-lithium in hexane and stirred at −70° C. for one hour. The reaction mixture is then admixed with 0.19 g (6 mmol) of sulphur powder and stirred at −70° C. for 4 hours. The mixture is subsequently hydrolyzed at −70° C. by addition of 1 ml of methanol and 1 ml of acetic acid. The reaction mixture is initially diluted with ethyl acetate and then extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. The resulting crude product (1.7 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 0.5 g (32% of theory) of 1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-[(5-mercapto-1,2,4-triazol-1-yl)-methyl]-1-pentene is obtained in the form of a solid substance of melting point 162-164° C.

The compounds listed in Table 13 below are also prepared by the methods given in Examples 13 and 14.

TABLE 12 (II-b)

Ex. Comp. Physical No. No. R² R³ constant 15 (II-3) —CCl═CHCl —C(CH₃)₃ mp. 168- 169° C. 16 (II-4)

GC/MS (Cl):376 (M + H⁻) 17 (II-5)

mp. 163- 164° C. 18 (II-6)

—C(CH₃)₃ mp. 127° C. 19 (II-7)

Oil 20 (II-8)

GC/MS (Cl):340 (M + H⁻) 21 (II-9)

GC/MS (Cl):424 (M + H⁻) 22 (II-10)

mp. 168° C. 23 (II-11)

GC/MS (Cl):314 (M + H⁺) 24 (II-12)

GC/MS (Cl):346 (M + H⁺) 25 (II-13)

mp. 115- 118° C. 26 (II-14)

—C(CH₃)₃ GC/MS (Cl):340 (M + H⁺) 27 (II-15)

GC/MS (Cl):334 (M + H⁻) 28 (II-16)

—C₄H₉-n *)

The compound is characterized by the following signals in the ¹H NMR spectrum (400 MHz, CDCl₃/TMS); δ=0.8 (t, 3H); 0.85 (m, 2H); 1.25 (m, 2H); 1.8 (m, 1H); 2.55 (m, 1H); 4.6 (OH); 4.9 (AB, 2H); 7.2 (dd, 1H); 7.35 (d, 1H); 7.7 (s, 1H); 7.75 (d, 1H); 12.3 (5H) ppm.

Example 29

At −70° C., a mixture of 1.3 g (4 mmol) of 3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-(1,2,4-triazol-1-yl-methyl)-oxirane (Z form) and 25 ml of absolute tetrahydrofuran is admixed with 2.0 ml (5 mmol) of n-butyl-lithium in hexane and stirred at −70° C. for 1 hour. The reaction mixture is then admixed with 0.16 g (5 mmol) of sulphur powder and stirred at −70° C. for 4 hours. Subsequently, 1 ml of methanol and 1 ml of acetic acid are simultaneously added dropwise with stirring at −70° C. The resulting mixture is diluted with dichloromethane and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (1.9 g) which, according to the gas chromatogram, contains 51.0% of the desired product in addition to 20.7% of starting material, is recrystallized from toluene. In this manner, 0.8 g (55% of theory) of 3-(2-chlorophenyl)-2-(4-fluoro-phenyl)-2-(5-mercapto-1,2,4-triazol-1-yl-methyl)-oxirane (Z form) is obtained as a solid substance of melting point 179 to 180° C.

¹H NMR spectrum (200 MHz, CDCl₃, TMS): δ=3.7 (d, J=15 Hz, 1H); 4.1 (s, 1H); 5.15 (d, J=15 Hz, 1H); 6.95-7.6 (m, 8H); 7.65 (s, 1H); 11.0 (s, 1H) ppm. GC/MS (ci): 362 (M+H⁺).

Example 30

At −20° C., a mixture of 1.6 g (5 mmol) of 5-(4-chlorobenzyl)-2,2-dimethyl-1-(1,2,4-triazol-1-yl-methyl)-cyclopentane-1-ol (Z form) and 30 ml of absolute tetrahydrofuran is admixed with 4 ml (10 mmol) of n-butyl-lithium in hexane, and stirring is continued at 0° C. for 30 minutes. The reaction mixture is subsequently cooled to −70° C., admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at −70° C. for 1 hour and subsequently at 0° C. for 2 hours, The resulting mixture is diluted with ethyl acetate and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (2.0 g) is recrystallized from toluene. In this manner, 1.1 g (63% of theory) of 5-(4-chloro-benzyl)-2,2-dimethyl-1-(5-mercapto-1,2,4-triazol-1-yl-methyl)-cyclopentan-1-ol (Z form) are obtained as a solid substance of melting point 179 to 180° C.

GC/MS (ci): 352 (M+H⁺).

Example 31

At −20° C. a mixture of 1.59 g (5 mmol) of 2-(4-chloro-benzylidene)-5,5-dimethyl-1-(1,2,4-triazol-1-yl-methyl)-cyclopentan-1-ol and 30 ml of absolute tetrahydrofuran is admixed with 4.4 ml (11 mmol) of n-butyl-lithium in hexane, and stirring is continued at 0° C. for 30 minutes. The reaction mixture is subsequently cooled to −70° C. admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at −20° C. for 1 hour and subsequently at 0° C. for 2 hours. The resulting mixture is diluted with ethyl acetate and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (1.9 g) is chromatographed over silica gel using ethyl acetate. In this manner, 0.8 g (46% of theory) of 2-(4-chloro-benzylidene)-5,5-dimethyl-1-(5-mercapto-1,2,4-triazol-1-yl-methyl)-cyclopentan-1-ol is obtained.

¹H-NMR spectrum (200 MHz, CDCl₃, TMS): δ=0.9 (s,3H); 1.15 (s,3H); 1.6-1.95 (m,2H); 2.4-3.0 (m,2H); 4.25 (d,1H); 4.55 (d,1H); 5.9 (m, 1H); 7.1-7.3 (m, 4H); 7.6 (s, 1H) ppm.

Example 32

At −20° C. a mixture of 1.53 g (5 mmol) of 2-(2,4-difluoro-phenyl)-1,3-bis-(1,2,4-triazol-1-yl)-propan-2-ol and 30 ml of absolute tetrahydrofuran is admixed with 4,4 ml (11 mmol) of n-butyl-lithium in hexane, and stirring is continued at 0° C. for 30 minutes. The reaction mixture is subsequently cooled to −70° C., admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at −70° C. for 1 hour and subsequently at 0° C. for 2 hours. The resulting mixture is diluted with ethyl acetate and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (2,3 g) is purified by silica gel chromatography using a mixture of ethyl acetate and ethanol=9:1 as mobile phase. In this manner, 1.0 g (59% of theory) of 2-(2,4-difluoro-phenyl)-1-(5-mercapto-1,2,4-triazol-1-yl)-3-(1,2,4-triazol-1-yl)-propan-2-ol is obtained in the form of a solid substance of melting point 187° C.

GC/MS (ci): 339 (M+H⁺).

Example 33

At −20° C., a mixture of 1.72 g (5 mmol) of 2,2-dimethyl-3-hydroxy-4-(1,2,4-triazol-1-yl)-1-(4-trifluoromethoxy-phenyl)-pentane and 30 ml of absolute tetrahydrofuran is admixed with 4,4 ml (11 mmol) of n-butyl-lithium in hexane, and stirring is continued at 0° C. for 30 minutes. The reaction mixture is subsequently cooled to −70° C., admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at −70° C. for 1 hour and subsequently at 0° C. for 2 hours. The resulting mixture is diluted with ethyl acetate and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (2.2 g) is purified by silica gel chromatography using a illixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 1.4 g (75% of theory) of 2,2-dimnethyl-3-hydroxy-4-(5-mercapto-1,2,4-triazol-1-yl)-1-(4-trifluoromethoxy-phenyl)-pentane are obtained in the form of a solid substance of melting point 125 to 126° C.

GC/MS(ci): 376 (M+H⁺).

Example 34

At −20° C., a mixture of 1.48 g (5 mmol) of 1-(4-chloro-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-ol and 30 ml of absolute tetrahydrofuran is admixed with 4 ml (10 mmol) of n-butyl-lithium, and stirring is continued at −20° C. for 30 minutes. At −20° C. the reaction mixture is then admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at −20° C. for 1 hour and subsequently at 0° C. for 2 hours. The resulting mixture is diluted with ethyl acetate and extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (1.9 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 0.7 g (43% of theory) of 1-(4-chlorophenoxy)-1-(5-mercapto-1,2,4-triazol-1-yl)-3.3-dimethyl-butan-2-ol is obtained in the form of a solid substance of melting point 193 to 194° C.

MS(ci): 328 (M+H⁺).

Example 35

with stirring, a mixture of 2.0 g (5 mmol) of 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-(1,2,4-triazol-1-yl-methyl)-4-methyl-1,3-dioxolan, 0.32 g (10 mmol) of sulphur powder and 10 ml of absolute N-methylpyrrolidone is heated at 200° C. for 22 hours. The reaction mixture is subsequently concentrated under reduced pressure (0.2 mbar). The remaining residue is admixed with ethyl acetate, and the resulting mixture is extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (1.8 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 0.9 g (41% of theory) of 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-[(5-mercapto-1,2,4-triazol-1-yl)-methyl]-4-methyl-1,.3-dioxolan is obtained in the form of an isomer mixture.

MS (ci): 438 (M+H⁺, 100%).

Example 36

Under an atmosphere of nitrogen and with stirring, a mixture of 1.42 g (5 mmol) of 2-(2,4-dichloro-phenyl)-1-(1,2,4-triazol-1-yl)-pentane, 0.32 g (10 mmol) of sulphur powder and 10 ml of absolute N-methylpyrrolidone is heated at 200° C. for 3 hours. The reaction mixture is subsequently concentrated under reduced pressure. The remaining residue is admixed with ethyl acetate, and the resulting mixture is extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (2.1 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 1.5 g (95% of theory) of 2-(2,4-dichloro-phenyl)-1-(5-mercapto-1,2,4-triazol-1-yl)-pentane are obtained in the form of a solid substance of melting point 103° C.

Example 37

Under an atmosphere of nitrogen and with stirring, a mixture of 2,93 g (10 mmol) of 1-(4-chloro-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-one, 0.64 g (20 mmol) of sulphur powder and 10 ml of absolute N-methylpyrrolidone is heated at 200° C. for 8 hours. The reaction mixture is subsequently concentrated under reduced pressure and, the remaining residue is dissolved in dichloromethane. The resulting mixture is extracted repeatedly with saturated aqueous ammonium chloride solution.

The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (2.7 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 2.0 g (62% of theory) of 1-(4-chlorophenoxy)-1-(5-mercapto-1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-one are obtained in the form of a solid substance of melting point 134 to 136° C.

Example 38

Under an atmosphere of nitrogen and with stirring, a mixture of 1.68 g (5 mmol) of 4-(4-chloro-phenyl)-2-cyano-2-phenyl-1-(1,2,4-triazol-1-yl)-butane, 0.32 g (10 mmol) of sulphur powder and 10 ml of absolute N-methylpyrrolidone is heated at 200° C. for 47 hours. The reaction mixture is subsequently concentrated under reduced pressure, and the remaining residue is dissolved in ethyl acetate. The resulting mixture is extracted repeatedly with saturated aqueous ammonium chloride solution. The organic phase is dried over sodium sulphate and then concentrated under reduced pressure. The resulting crude product (1.9 g) is purified by silica gel chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as mobile phase. In this manner, 0.7 g (38% of theory) of 4-(4-chloro-phenyl)-2-cyano-2-phenyl-1-(5-mercapto-1,2,4-triazol-1-yl)-butane is obtained in the form of an oil.

¹H NMR spectrum (400 NMz, CDCl₃, TMS): δ=2.4 (m, 3H); 2.75 (m, 1H); 4.5 (AB, 2H); 7.0 (d, 2H); 7.2 (d, 2H); 7.4 (m, 3H); 7.55 (m, 2H); 7.8 (s, 1H) 11.7 (1H) ppm.

USE EXAMPLES Example A

Pseudocercosporella herpotrichoides test/W strain; (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate.

After the spray coating has dried on, the plants are inoculated at the base of the stem with spores of the W strain of Pseudocercosporella herpotrichoides.

The plants are placed in a greenhouse at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 80%.

Evaluation is carried out 21 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

In this test, the compound (I-9) disclosed in Example 9 exhibits, at an application rate of 250 g/ha, an efficacy of 100%.

TABLE A Peuedocercosporella herpotrichoides test/W strain; (wheat)/protective Application rate of active compound in Active compound g/ha Efficacy in % According to the invention:

250 100

Example B

Erysiphe test (barley)/curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for curative activity, young plants are dusted with spores of Erysiphe graminis F.sp. hordei, 48 hours after the inoculation, the plants are sprayed with the preparation of active compound at the stated application rate.

The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%, to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

In this test, the compounds (I-1) and (I-7) disclosed in Examples 1 and 7 exhibit, at an application rate of 250 g/ha, an efficacy of 100%.

TABLE B Erysiphe test (barley)/curative Application rate of active compound in Active compound g/ha Efficacy in % According to the invention:

250 100

250 100

Example C

Erysiphe test (barley)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate.

After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%, to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

In this test, the compounds (I-1) and (I-7) disclosed in Examples 1 and 7 exhibit, at an application rate of 250 g/ha, an efficacy of 100%.

TABLE C Erysiphe test (barley)/protective Application rate of active compound in Efficacy in Active compound g/ha % According to the invention:

250 100

250 100

Example D

Podosphaera test (apple)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the causative organism of apple mildew Podosphaera leucotricha. The plants are placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

Evaluation is carried out 10 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

Active compounds, active compound concentrations and test results are shown in the table below.

TABLE D Podosphaera test (apple)/protective Application rate of active compound in Efficacy in Active compound g/ha % According to the invention:

50 100

50 100

Example E

Sphaerotheca test (cucumber)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

Evaluation is carried out 10 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

Active compounds, active compound concentrations and test results are shown in the table below.

TABLE E Sphaerotheca test (cucumber)/protective Application rate of active compound in Efficacy in Active compound g/ha % According to the invention:

50 100

50 100

Example F

Venturia test (apple)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causative organism of apple scab Venturia inaequalis and then remain in an incubation cabin at approximately 20° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at approximately 21° C. and at a relative atmospheric humidity of approximately 90%.

Evaluation is carried out 12 days after the inoculation, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

Active compounds, active compound concentrations and test results are shown in the table below.

TABLE F Venturia test (apple)/protective Application rate of active compound in Efficacy in Active compound g/ha % According to the invention:

50 100

50 100

50 100

Example G

Botrytis test (bean)/protective

Solvent: 47 parts by weight of acetone Emulsifier:  3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, two small pieces of agar overgrown with Botrytis cinerea are placed onto each leaf. The inoculated plants are placed in a dark chamber at approximately 20° C. and 100% relative atmospheric humidity.

2 days after the inoculation, the size of the infested area on the leaves is evaluated, 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed.

Active compounds, active compound concentrations and test results are shown in the table below.

TABLE G Botrytis test (bean)/protective Application rate of active compound in Efficacy in Active compound g/ha % According to the invention:

500 100 

What is claimed is:
 1. An acyl-mercapto-triazolyl derivative of the formula

wherein R represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety which is unsubstituted or mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 12 carbon atoms, straight-chain or branched alkylamino having 1 to 14 carbon atoms or represents phenylamino which is unsubstituted or mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, and R¹ represents a radical of the formula

wherein R⁴ represents alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, unsubstituted or halogen-substituted cycloalkyl having 3 to 7 carbon atoms, naphthyl or phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, nitro, phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, and R⁵ represents phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms.
 2. An acyl-mercapto-triazolyl derivative of the formula:


3. A microbicidal composition comprising a microbicidally effective amount of a compound as claimed in claim
 1. 4. A method for controlling undesirable microorganisms in plant protection and in the preservation of materials, comprising the step of applying a microbicidally effective amount of a compound as claimed in claim 1 to the microorganisms and/or to their habitat. 